US4274985A - Cyclodextrin-polyvinyl alcohol polymers and a process for the preparation thereof in a pearl, foil, fiber or block form - Google Patents
Cyclodextrin-polyvinyl alcohol polymers and a process for the preparation thereof in a pearl, foil, fiber or block form Download PDFInfo
- Publication number
- US4274985A US4274985A US06/055,536 US5553679A US4274985A US 4274985 A US4274985 A US 4274985A US 5553679 A US5553679 A US 5553679A US 4274985 A US4274985 A US 4274985A
- Authority
- US
- United States
- Prior art keywords
- cyclodextrin
- polyvinyl alcohol
- polymer
- cyclodextrins
- polyvinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
Definitions
- This invention relates to new cyclodextrinpolyvinyl alcohol polymers capable of forming inclusion complexes and a process for the preparation thereof in a pearl, foil, fiber or block form.
- Cyclodextrins are non-reducing cyclic dextrins having a well-defined inner diameter and are capable of forming inclusion complexes. They consist of D-glucose units, which are connected with each other by ⁇ -1,4-bonds ⁇ -Cyclodextrin comprises 6, ⁇ -cyclodextrin 7 and ⁇ -cyclodextrin 8 ⁇ -D-glucose units.
- cyclodextrins By reacting with suitable polyfunctional compounds cyclodextrins can be converted into macromolecular compounds, which favorably combine the complex forming capability of cyclodextrins with the properties of polymeric compounds.
- inclusion resins comprising cyclodextrins dispersed in water-insoluble synthetic polymers (e.g. polyamide, polyvinyl acetate, polyacryl amide) is also described.
- water-insoluble synthetic polymers e.g. polyamide, polyvinyl acetate, polyacryl amide
- cyclodextrins are not bound chemically.
- polymers containing cyclodextrins form inclusion complexes with molecules having a suitable size and shape.
- Said inclusion complexes can generally be prepared from aqueous solutions. Due to their complex forming property water-insoluble cyclodextrin polymers can be advantageously and economically used, for example, for the separation and enrichment of various substances from aqueous solutions; for the stabilization of substances prone to decomposition in the form of their inclusion complexes; for application in inclusion chromatography; for smoke filtration; and as catalysts to accelerate various reactions.
- Complexes formed with cyclodextrin polymers can be separated from their solutions by conventional techniques, such as filtration or sedimentation, and the polymers can easily be regenerated and recycled.
- the present invention aims at the preparation of cyclodextrin-polyvinyl alcohol polymers in the form of pearls, foils, fibers or blocks, which are well swellable in aqueous solutions and are solid also in a swelled state, are elastic and have a good retentivity, are chemically stable, preserve their original properties during repeated use, purification and drying, are resistant to microorganisms and due to the above-listed properties can be used for complex formation more advantageously than related preparations known in the art.
- This invention relates to cyclodextrin-polyvinyl alcohol polymers, which can be formulated as pearls, fibers, blocks or foils.
- a process for the preparation of new cyclodextrin-polyvinyl alcohol polymers capable of forming inclusion complexes in various forms comprises cross-linking a cyclodextrin or a mixture of various cyclodextrins or carbohydrate mixtures containing cyclodextrins with a suitable polyfunctional reactant capable of reaction with cyclodextrin in the presence of polyvinyl alcohol, polyvinyl acetate or polyvinyl alcohol-acetate copolymer.
- Suitable representatives of polyfunctional reactants are the epoxy-compounds, such as epichlorohydrin, or diepoxy-compounds, e.g. ethylene glycol diepoxy polyether.
- Either epoxy or diepoxy compounds are used for the polymerization, the reaction is expediently carried out in an aqueous alkaline solution. Under these conditions the epoxide group can be hydrolyzed to hydroxyl, which can react with further epichlorohydrine or diepoxide molecules to afford a product in which the cyclodextrin-cyclodextrin, cyclodextrin-polyvinyl alcohol and polyvinyl alcohol-polyvinyl alcohol cross-bonds can be of different lengths.
- cyclodextrin-polyvinyl alcohol polymers can be obtained as pearls, foils, fibers or blocks. In this respect the degree of polymerization is entirely irrelevant since cross-linked products consisting of a single molecule are obtained.
- Pearl polymers can be obtained in a suspension. If a cyclodextrin-polyvinyl alcohol polymer is to be prepared, as a dispersion medium, a solvent restrictedly miscible with the reaction medium, preferably a hydrocarbon, such as toluene, and an emulsifying agent, preferably a solution of polyvinyl acetate (PVAc) can be used.
- a solvent restrictedly miscible with the reaction medium preferably a hydrocarbon, such as toluene
- an emulsifying agent preferably a solution of polyvinyl acetate (PVAc)
- the reaction medium is a solution prepared with a polar solvent, preferably water, which contains cyclodextrin ( ⁇ -, ⁇ - or ⁇ -cyclodextrin) or a mixture of cyclodextrin homologs of a carbohydrate mixture containing cyclodextrins, 0.1-10% of polyvinyl alcohol or a polyvinyl alcohol-acetate copolymer, and a catalyst, preferably a base.
- the concentration of the base depends on the cross-linking reactant (polyfunctional compound). For instance if epichlorohydrine is used, the concentration thereof preferably amounts to 10 to 20%, while the amount of ethylene glycol diepoxy propyl ether preferably is between 2 and 4%.
- the solution is dispersed in a dispersion medium with stirring, under conditions providing a suspension having a desired dispersity grade. Thereafter the polyfunctional cross-linking agent is added into the system in one portion or gradually, within a predetermined time, and the reaction is carried out under suitable conditions, with stirring. Varying the cyclodextrin to a coupling agent ratio between 1:3 and 1:10, a solid, regular spherical product is obtained, which has a good retentivity and can be settled when the reaction terminates. It is then preferably washed with solvents and is subsequently dried. If the dispersion phase contains polyvinyl acetate, polyvinyl alcohol incorporates into the product even then, when no polyvinyl alcohol was introduced into the reaction medium.
- the cyclodextrin concentration in the cyclodextrin-polyvinyl alcohol pearl polymer prepared as described above can be as high as 50 to 70%, its water uptake can be varied between 1 and 5 g. of water/g. of resin, and the product can be used for the preparation of inclusion complexes with suitable components of solutions, gases or vapors. It is especially suitable for the purification of industrial waste waters and for use in inclusion chromatography. From aqueous solutions, for example, benzene and chloroform traces can be eliminated in this manner. From waste waters, especially p-cresol and O,O-dimethyl-1-hydroxy-2,2,2-trichloroethyl, phosphate can easily be eliminated by the above-described polymers.
- cyclodextrin ⁇ -, ⁇ - or ⁇ -cyclodextrin
- a mixture of cyclodextrin homologs, or a cyclodextrin-containing carbohydrate mixture is suitably dissolved in a solution of 5 to 15% of polyvinyl alcohol in a polar solvent, preferably in an aqueous alkaline solution.
- cyclodextrin-polyvinyl alcohol foils produced by this method are especially well swellable in water, are elastic in a swelled state, are not rigid and are flexible. Cyclodextrin-polyvinyl alcohol foils can contain up to 40 to 50% of cyclodextrin-and are capable of forming inclusion complexes from solutions.
- Polymer fibers can be prepared by two methods. According to the first one, the procedure described for the preparation of foils is followed except that the viscous solution is not poured onto a flat surface, instead it is introduced into a precipitation bath where fibers are pulled. As a precipitation bath preferably a saturated solution of sodium sulphate is used. According to an alternative method, a solution containing polyvinyl alcohol and a coupling agent is introduced into a precipitation bath which also contains a water-soluble polymer prepared starting from cyclodextrin ( ⁇ -, ⁇ - or ⁇ -cyclodextrin) or from a mixture of cyclodextrin homologs or from a cyclodextrin-containing carbohydrate mixture (British patent specification No.
- the polyvinyl alcohol concentration of the solution should preferably be 15 to 17%.
- the product obtained is washed and thereafter is subjected to heat treatment.
- Flexible, well swellable fibers are obtained, which contain 5 to 15% of cyclodextrin and are capable of forming inclusion complexes from solutions.
- Block polymers are prepared starting from various solutions containing polyvinyl alcohol, cyclodextrin ( ⁇ , ⁇ - or ⁇ -cyclodextrin), a mixture of cyclodextrins or a mixture of cyclodextrin and carbohydrates as well as a polyfunctional reactant.
- the product obtained is washed, dried and finally is pulverized.
- the powder obtained has a high specific surface, a good filterability, it is easy to handle and can be used for the formation of inclusion complexes from solutions, gases or vapors.
- the swellability of the block polymer obtained can be varied within a wide range, depending on the mutual propportions of the components.
- the toluene phase is decanted and the sedimented grains are suspended in a further portion of toluene, settled down, and decanted. Thereafter the product is washed with acetone three subsequent times, followed by washing to neutral with water. The pearl polymer obtained is then dehydrated with a more concentrated acetone/water mixture and is allowed to stand in acetone for at least two hours. Thereafter it is dried in an desiccator at 105° C. for three hours. 6 g. of a polymeric product are obtained containing 45% of cyclodextrin and 0.8% of polyvinyl alcohol. The water uptake (swelling capacity) of the product is 2 g. of water/g. of dry gel; specific volume of the swelled gel: 6 ml./g.
- the product was characterized by analytical methods developed for the characterization of cyclodextrin-polyvinyl alcohol polymers, first of all by a microscopic method or by quantitative analysis of the cyclodextrin and polyvinyl alcohol content, respectively or by measuring the water uptake and the specific volume of the swelled gel.
- Example 2 Following the procedure described in Example 1 but dissolving 1 g. (0.0009 moles) of ⁇ -cyclodextrin in a 5% alkaline solution of polyvinyl alcohol and adding 1.5 ml. (1.1 g.; 0.010 moles) of ethylene glycol diepoxy propyl ether to the mixture a pearl polymer is obtained, containing 40% of cyclodextrin and 15% of polyvinyl alcohol.
- the water uptake of the product amounts to 5 g. of water/g. of gel and the volume of the swelled gel is 20 ml./g.
- Example 2 Following the procedure described in Example 1 but dissolveing 4 g. (0.0031 moles) of ⁇ -cyclodextrin in 6 ml. of a 1 N sodium hydroxide solution and adding 4 ml. (0.026 moles) of ethylene glycol diepoxy propyl ether a pearl polymer is obtained, containing 50% of ⁇ -cyclodextrin and 0.5% of polyvinyl alcohol.
- the water uptake of the product amounts to 2.5 g. of water/g. of gel and the specific volume of the swelled gel is 7 ml./g.
- a solution containing cyclodextrin and polyvinyl alcohol is admixed with 2 ml. of a solution of 1 g. (0.0009 moles) of ⁇ -cyclodextrin in a 1 N sodium hydroxide solution at 80° C. with stirring.
- 1 ml. (0.0064 moles) of ethylene glycol diepoxy propyl ether is added and the mixture is poured onto a flat surface before solidification. It is allowed to stand at room temperature for a day, the foil obtained is rinsed in water several more times and is air dried.
- the product obtained contains 40% of ⁇ -cyclodextrin and its water uptake is 4 g. of water/g. of dry polymer.
- a cyclodextrin-polyvinyl alcohol polymer fibers is obtained by heating a mixture of 10 ml. of polyvinyl alcohol and a 1 N alkaline solution containing 15% of polyvinyl alcohol and 3--3% of ⁇ -cyclodextrin and ethylene glycol diepoxy and propyl ether at 80° C., and before the mixture becomes gelled it is introduced into a 20% sodium sulphate precipitation bath and fibers are pulled.
- the product contains 6% of cyclodextrin.
- a cyclodextrin-polyvinyl alcohol polymer fibers is obtained by admixing 5% of ethylene glycol diepoxy propyl ether in a solution containing 15% of polyvinyl alcohol at 70° C. and introducing the mixture obtained into the precipitation bath of 30° C.
- the bath contains 20% of sodium sulphate, 10% of water-soluble ⁇ -cyclodextrin polymer and 2% of sodium hydroxide.
- the fiber is allowed to stand in the bath for 5 minutes, whereupon it is heated up to 105° C., washed and dried.
- the obtained fibrous product contains 13% of cyclodextrin.
- the grain distribution of the pearl polymer obtained in Example 1 is determined in a dry state.
- the mean size on the basis of the number of particles is 53 ⁇ , while the means size on the basis of the volume of grains is 67 ⁇ .
- the product is swelled for one day. In a swelled state the mean grain size on the basis of the number of grains is 85 ⁇ , while on the basis of the volume of grains it amounts to 107 ⁇ .
- the polymer is then dried and swelled several more times and the mean size of the grains is determined after every period.
- the distribution does not show any significant difference even after the 10th period, when the mean grain size on the basis of the number of grains for a dry product is 53 ⁇ , for a swelled product is 84 ⁇ , and the same value on the basis of the volume of particles amounts to 56 ⁇ for the dry polymer and 107 ⁇ for the swelled polymer.
- a mixture of 3 mg. of aliphatic amino acid mixture (glycine, alanine, valine, leucine, isoleucine, serine, threonine, ciysteine, methionine, asparaginic acid, glutaminic acid, lysine, arginine, histidine, proline and hydrosyproline), 0.1 mg. of phenylamine and 0.3 mg. of tryptophan is subjected to column chromatography. The elution is carried out by distilled water, at a rate of 40 ml./hour. [V 3 /V t ] tryptophan: 2.40, phenylaminine: 1.10; mixture of aliphatic amino acids: 0.73.
- Example 2 With a pearl polymer prepared according to Example 1, a column of 1.2 cm. ⁇ 20 cm. is filled and 50 ml of a 0.07% aqueous benzene solution is passed through it at a rate of 40 ml./hour. The water leaving the column is benzene-free. The benzene bound in the complex is elminated by boiling. The polymer can be regenerated and used repeatedly.
- Cyclodextrin-polyvinyl alcohol block polymer is prepared in the following way:
- Example 2 the suspension is triturated and water is decanted.
- the polymer is washed with two 100-ml. portions of water. Dehydration is carried out as described in Example 1, using acetone/water mixtures of increasing concentrations.
- the product is dried at 105° C. 21 g. of a polymeric product are obtained, containing 47% of cyclodextrin and 4.5% of polyvinyl alcohol.
- the water uptake of the product amounts to 2.2 g. of water/g. of dry polymer, and the specific volume of the swelled product is 5.2 ml./g.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Artificial Filaments (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Nonwoven Fabrics (AREA)
- Medicinal Preparation (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HUCI1845 | 1978-07-13 | ||
HU78CI1845A HU177419B (en) | 1978-07-13 | 1978-07-13 | Process for preparing threedimensional,retentive polymers consisting of cyclodextrin and polyvinylalcohol units,capable of forming inclusion complexes in the form of bead,fibre or mainly block |
Publications (1)
Publication Number | Publication Date |
---|---|
US4274985A true US4274985A (en) | 1981-06-23 |
Family
ID=10994703
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/055,536 Expired - Lifetime US4274985A (en) | 1978-07-13 | 1979-07-09 | Cyclodextrin-polyvinyl alcohol polymers and a process for the preparation thereof in a pearl, foil, fiber or block form |
Country Status (17)
Country | Link |
---|---|
US (1) | US4274985A (da) |
JP (1) | JPS5820962B2 (da) |
AT (1) | AT369402B (da) |
BE (1) | BE877653A (da) |
CA (1) | CA1124928A (da) |
CH (1) | CH644386A5 (da) |
CS (1) | CS214764B2 (da) |
DD (1) | DD145108A1 (da) |
DE (1) | DE2927733C2 (da) |
DK (1) | DK166028C (da) |
FI (1) | FI65444C (da) |
FR (1) | FR2430954A1 (da) |
GB (1) | GB2030574B (da) |
HU (1) | HU177419B (da) |
NO (1) | NO153967C (da) |
SE (1) | SE446453B (da) |
SU (1) | SU1227118A3 (da) |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1982000251A1 (en) * | 1980-07-21 | 1982-02-04 | Commerce Us | Water soluble form of retinoids |
US4365061A (en) * | 1980-10-17 | 1982-12-21 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara R.T. | Inclusion complexes of cyclodextrins and strong inorganic oxy-acids and process for their preparation |
WO1983000809A1 (en) * | 1981-09-09 | 1983-03-17 | Chinoin Gyogyszer Es Vegyeszet | Method for the preparation of tablets which rapidly disintegrate in an aqueous medium |
US4547572A (en) * | 1983-02-04 | 1985-10-15 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt. | Cyclodextrin polymers swelling quickly and to a great extent in water and process for the preparation thereof |
US4726905A (en) * | 1986-04-30 | 1988-02-23 | American Maize-Products Company | Method for removing polychlorinated biphenyl compounds from water |
US4774329A (en) * | 1987-08-04 | 1988-09-27 | American Maize-Products Company | Controlled release agent for cetylpyridinium chloride |
DE3819498A1 (de) * | 1987-06-08 | 1988-12-29 | Consortium Elektrochem Ind | Cyclodextrinpolymerjodeinschlussverbindungen mit kontrollierter jodfreisetzung |
WO1990002141A1 (en) * | 1988-08-31 | 1990-03-08 | Australian Commercial Research & Development Limited | Compositions and methods for drug delivery and chromatography |
US5075432A (en) * | 1989-08-11 | 1991-12-24 | Edward Vanzo | Spherical cyclodextrin polymer beads |
US5276088A (en) * | 1990-05-21 | 1994-01-04 | Toppan Printing Co., Ltd. | Method of synthesizing cyclodextrin polymers |
US5487998A (en) * | 1993-01-06 | 1996-01-30 | The United States Of America As Represented By The Secreatry Of The Department Of Health And Human Services | Trapping of aflatoxins and phytoestrogens |
US5492947A (en) * | 1994-06-23 | 1996-02-20 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
US5608015A (en) * | 1990-11-30 | 1997-03-04 | Toppan Printing Co., Ltd. | Processes for producing cyclodextrin derivatives and polymers containing immobilized cyclodextrin therein |
US5776842A (en) * | 1994-06-23 | 1998-07-07 | Cellresin Technologies, Llc | Cellulosic web with a contaminant barrier or trap |
US5882565A (en) * | 1995-12-11 | 1999-03-16 | Cellresin Technologies, Llc | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
US5928745A (en) * | 1994-06-23 | 1999-07-27 | Cellresin Technologies, Llc | Thermoplastic fuel tank having reduced fuel vapor emissions |
US5985772A (en) * | 1994-06-23 | 1999-11-16 | Cellresin Technologies, Llc | Packaging system comprising cellulosic web with a permeant barrier or contaminant trap |
US6527887B1 (en) | 2002-01-18 | 2003-03-04 | Mach I, Inc. | Polymeric cyclodextrin nitrate esters |
WO2005078028A1 (en) * | 2004-02-05 | 2005-08-25 | Millipore Corporation | Method of forming polysaccharide structures |
WO2005078016A1 (en) * | 2004-02-05 | 2005-08-25 | Millipore Corporation | Room temperature stable agarose solutions |
US20050191426A1 (en) * | 2004-02-05 | 2005-09-01 | Wilson Moya | Method of forming coated structures |
US20050211615A1 (en) * | 2004-02-05 | 2005-09-29 | Millipore Corporation | Porous adsorptive or chromatographic media |
US20050211616A1 (en) * | 2004-02-05 | 2005-09-29 | Millipore Corporation | Porous adsorptive or chromatographic media |
US20050276841A1 (en) * | 2004-06-07 | 2005-12-15 | California Institute Of Technology | Biodegradable drug-polymer delivery system |
US20090050566A1 (en) * | 2007-08-14 | 2009-02-26 | Mikhail Kozlov | Media for membrane ion exchange chromatography based on polymeric primary amines, sorption device containing that media, and chromatography scheme and purification method using the same |
US20090130738A1 (en) * | 2007-11-19 | 2009-05-21 | Mikhail Kozlov | Media for membrane ion exchange chromatography |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4426292A (en) | 1982-02-19 | 1984-01-17 | Exxon Research And Engineering Co. | Process for selective separation of molecular species from mixtures thereof using cyclodextrins |
JPH072771B2 (ja) * | 1984-06-27 | 1995-01-18 | ナシヨナル・スタ−チ・アンド・ケミカル・コ−ポレイシヨン | グルコシド側鎖を有する合成重合体の製造方法 |
US4808232A (en) * | 1986-12-08 | 1989-02-28 | American Maize-Products Company | Separation and purification of cyclodextrins |
DE4009840A1 (de) * | 1990-03-27 | 1991-10-02 | Consortium Elektrochem Ind | Cyclodextrin-polymerisate und verfahren zu deren herstellung |
JPH06165988A (ja) * | 1992-08-24 | 1994-06-14 | J Shii S:Kk | 塗料スラッジ回収が容易な静電凝集器付水洗式塗装ブース |
DE19612768A1 (de) * | 1996-03-29 | 1997-10-02 | Basf Ag | Cyclodextringruppen enthaltende Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung |
WO2012120905A1 (ja) * | 2011-03-09 | 2012-09-13 | 国立大学法人北海道大学 | 架橋型金属有機構造体および有機物架橋体、およびそれらの製造方法 |
AU2020204925A1 (en) | 2019-01-03 | 2021-07-22 | Cyclarity Therapeutics, Inc. | Cyclodextrin dimers, compositions thereof, and uses thereof |
Citations (2)
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US3420788A (en) * | 1964-04-29 | 1969-01-07 | Afico Sa | Inclusion resins of cyclodextrin and methods of use |
GB1244990A (en) * | 1968-12-03 | 1971-09-02 | Avebe Coop Verkoop Prod | Cyclodextrin derivatives |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE358894B (da) * | 1961-10-25 | 1973-08-13 | Pharmacia Ab |
-
1978
- 1978-07-13 HU HU78CI1845A patent/HU177419B/hu not_active IP Right Cessation
-
1979
- 1979-07-06 AT AT0471279A patent/AT369402B/de not_active IP Right Cessation
- 1979-07-09 US US06/055,536 patent/US4274985A/en not_active Expired - Lifetime
- 1979-07-10 GB GB7923950A patent/GB2030574B/en not_active Expired
- 1979-07-10 DE DE2927733A patent/DE2927733C2/de not_active Expired
- 1979-07-11 FR FR7918012A patent/FR2430954A1/fr active Granted
- 1979-07-11 FI FI792180A patent/FI65444C/fi not_active IP Right Cessation
- 1979-07-12 CS CS794890A patent/CS214764B2/cs unknown
- 1979-07-12 SE SE7906088A patent/SE446453B/sv not_active IP Right Cessation
- 1979-07-12 NO NO792322A patent/NO153967C/no unknown
- 1979-07-12 BE BE0/196261A patent/BE877653A/xx not_active IP Right Cessation
- 1979-07-12 DK DK293379A patent/DK166028C/da not_active IP Right Cessation
- 1979-07-12 CH CH652179A patent/CH644386A5/de not_active IP Right Cessation
- 1979-07-12 DD DD79214293A patent/DD145108A1/de not_active IP Right Cessation
- 1979-07-12 SU SU792788604A patent/SU1227118A3/ru active
- 1979-07-13 CA CA331,763A patent/CA1124928A/en not_active Expired
- 1979-07-13 JP JP54088357A patent/JPS5820962B2/ja not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3420788A (en) * | 1964-04-29 | 1969-01-07 | Afico Sa | Inclusion resins of cyclodextrin and methods of use |
GB1244990A (en) * | 1968-12-03 | 1971-09-02 | Avebe Coop Verkoop Prod | Cyclodextrin derivatives |
Cited By (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1982000251A1 (en) * | 1980-07-21 | 1982-02-04 | Commerce Us | Water soluble form of retinoids |
US4371673A (en) * | 1980-07-21 | 1983-02-01 | The United States Of America As Represented By The Secretary Of The Department Of Health And Human Services | Water soluble forms of retinoids |
US4365061A (en) * | 1980-10-17 | 1982-12-21 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara R.T. | Inclusion complexes of cyclodextrins and strong inorganic oxy-acids and process for their preparation |
WO1983000809A1 (en) * | 1981-09-09 | 1983-03-17 | Chinoin Gyogyszer Es Vegyeszet | Method for the preparation of tablets which rapidly disintegrate in an aqueous medium |
US4547572A (en) * | 1983-02-04 | 1985-10-15 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt. | Cyclodextrin polymers swelling quickly and to a great extent in water and process for the preparation thereof |
US4726905A (en) * | 1986-04-30 | 1988-02-23 | American Maize-Products Company | Method for removing polychlorinated biphenyl compounds from water |
DE3819498A1 (de) * | 1987-06-08 | 1988-12-29 | Consortium Elektrochem Ind | Cyclodextrinpolymerjodeinschlussverbindungen mit kontrollierter jodfreisetzung |
US4774329A (en) * | 1987-08-04 | 1988-09-27 | American Maize-Products Company | Controlled release agent for cetylpyridinium chloride |
GB2208386A (en) * | 1987-08-04 | 1989-03-30 | American Maize Prod Co | Controlled release agent for cetylpyridinium chloride |
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Also Published As
Publication number | Publication date |
---|---|
FI65444B (fi) | 1984-01-31 |
FI792180A (fi) | 1980-01-14 |
CS214764B2 (en) | 1982-05-28 |
SE446453B (sv) | 1986-09-15 |
CA1124928A (en) | 1982-06-01 |
DK166028C (da) | 1993-07-12 |
GB2030574A (en) | 1980-04-10 |
JPS5820962B2 (ja) | 1983-04-26 |
GB2030574B (en) | 1983-03-23 |
CH644386A5 (de) | 1984-07-31 |
DK166028B (da) | 1993-03-01 |
AT369402B (de) | 1982-12-27 |
SE7906088L (sv) | 1980-01-14 |
FI65444C (fi) | 1984-05-10 |
BE877653A (fr) | 1979-11-05 |
FR2430954A1 (fr) | 1980-02-08 |
JPS5513796A (en) | 1980-01-30 |
DE2927733A1 (de) | 1980-01-31 |
NO792322L (no) | 1980-01-15 |
DK293379A (da) | 1980-01-14 |
DE2927733C2 (de) | 1986-03-27 |
SU1227118A3 (ru) | 1986-04-23 |
HU177419B (en) | 1981-10-28 |
ATA471279A (de) | 1982-05-15 |
DD145108A1 (de) | 1980-11-19 |
NO153967C (no) | 1986-06-25 |
NO153967B (no) | 1986-03-17 |
FR2430954B1 (da) | 1984-08-17 |
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